Dicyandiamide-formaldehyde condensates modified with urea and process for preparing the same

ABSTRACT

Disclosed are novel water-soluble, thermosettable resinous compositions derived by reacting a precondensate of dicyandiamide, formaldehyde, a salt of a water-soluble polyaminopolyamide and an ammonium salt with urea and then condensing the reaction product with additional formaldehyde. The resinous compositions are cationic and have particular utility in the manufacture of paper sized with cellulose reactive sizing agents such as ketene dimer sizing agents.

This invention relates to novel water-soluble, thermosettable resinouscompositions containing dicyandiamide-formaldehyde condensates and moreparticularly relates to the compositions produced by reacting aprecondensate of dicyandiamide, formaldehyde, an acid salt of awater-soluble polyaminopolyamide and an ammonium salt with urea, andthen condensing the reaction product with formaldehyde. The resinouscompositions are cationic and water-soluble and have particular utilityin the manufacture of sized paper wherein the sizing agent employed is acellulose reactive sizing agent such as a ketene dimer sizing agent.

In U.S. Pat. No. 3,840,486, Dumas describes water-soluble, cationic,thermosettable resinous compositions derived from dicyandiamide, anammonium salt, formaldehyde and an acid salt of a water-solublepolyaminopolyamide and teaches their preparation by forming aprecondensate by heat reacting in aqueous medium 1 mole ofdicyandiamide, from 0.75 to 1.5 moles of formaldehyde, sufficient of anacid salt of a polyaminopolyamide to provide about 0.125 to about 0.5equivalent of basic nitrogen and an ammonium salt in an amount toprovide a total of from 0.8 to about 1.2 equivalents of basic nitrogenuntil substantially all nitriles of the dicyandiamide have reacted,adding from about 1.25 to about 3.75 moles of formaldehyde to theaqueous precondensate and refluxing the resulting mixture until theviscosity of a solution of the product is within a desired range. Theresinous compositions of U.S. Pat. No. 3,840,486 are said to be usefulas accelerators for hydrophobic cellulose reactive sizing agents and thecombination is reported to provide higher off-the-machine sizing than isprovided by an equivalent amount of the sizing agent alone. Dumas'resinous compositions, however, do not impart sizing to paper when usedalone in amounts normally employed in the paper sizing art and the useof Dumas' resinous compositions in combination with cellulose reactivesizes as sizing agents in the manufacture of paper does not provide anultimate degree of sizing which is substantially different from thatachieved with the sizing agent alone. Since nearly all grades of paperare sized to some extent, increased sizing efficiency is an importantobjective of papermakers and any improvements which can be realized inthe degree of sizing can have pronounced economic significance.

Now, in accordance with this invention, it has been found that uniqueresins are produced by modifying the process of U.S. Pat. No. 3,840,486and that the modified resins so produced provide higher ultimate sizingwith cellulose reactive sizing agents such as ketene dimers, acidanhydrides and isocyanates on natural aging or oven curing as comparedwith the unmodified resins. Further, the resins produced in accordancewith this invention accelerate the rate of sizing development withcellulose reactive sizing agents and thus increase the overallefficiency of the sizing agents.

Accordingly, the present invention relates to a process for preparingimproved water-soluble thermosettable resinous compositions containingdicyandiamide-formaldehyde condensates, which process comprises (1)forming a precondensate solution by refluxing for about 1 to about 4hours an aqueous mixture of (a) a base reaction product of 1 mole ofdicyandiamide, 0.75 mole to 1.5 moles of formaldehyde and an acid saltof a water-soluble polyaminopolyamide in an amount sufficient to providefrom about 0.125 to about 0.5 equivalent of basic nitrogen and (b) anammonium salt in an amount such that there will be from 0.7 equivalentto about 1.2 equivalents of basic nitrogen derived from the salt of thepolyaminopolyamide and the ammonium salt in the aqueous medium, (2)adding to the precondensate solution from 0.30 to 0.45 mole of urea perequivalent of basic nitrogen derived from the salt of thepolyaminopolyamide and the ammonium salt, and heating the aqueousmixture at about 80° to about 110° C. for about 0.5 hour to about 1.5hours until a solution of modified precondensate is formed, (3) addingfrom about 1.25 to about 3.75 moles of formaldehyde to the aqueoussolution of modified precondensate and (4) heating the resulting mixtureat about 60° C. to about 100° C. until the viscosity of an aqueoussolution of the resulting reaction product at a solids content of 50% isfrom about U to Z on the Gardner-Holdt scale, and to the resinouscompositions so produced.

As above set forth, dicyandiamide is one of the reactants employed inpreparing the precondensate in the first step of the process of thisinvention. Dicyandiamide is also known as cyanoguanidine and has thefollowing structure: ##STR1##

Formaldehyde is another reactant employed to prepare the precondensate.As employed in this specification and in the claims, formaldehydeincludes formaldehyde in the form of 30-40% aqueous solutions andpolymeric forms of formaldehyde such as, for example, paraformaldehyde,trioxane, and hexamethylenetetramine. Chemical compounds such as acetalswhich will liberate formaldehyde on heating can be employed as a sourceof formaldehyde if desired.

The ammonium salt reactant is a water-soluble salt of an amine and anacid. Particularly suitable salts are those having the formula (NH₄)_(m)X; (R₁ NH₃)_(m) X; or (R₁ R₂ NH₂)_(m) X where R₁ and R₂ are alkylradicals having from 1 through 4 carbon atoms such as methyl, ethyl,propyl, isopropyl and n-butyl; X is the acid anion such, for example, asCl⁻, Br⁻, I⁻, SO₄ ⁼, CH₃ COO⁻, NO₃ ⁻, and PO₄.sup..tbd. ; and m is aninteger equal to the anion charge. Specific examples of suitableammonium salts include ammonium sulfate, ammonium chloride, methylammonium chloride, dimethyl ammonium chloride, ethyl ammonium sulfate,and ammonium acetate.

Other suitable ammonium salts are the water-soluble salts of (1) apolyamine having the structure ##STR2## where R₃ is hydrogen or methyl;n is an integer 2 through 6; and x is an integer 0 through 3 and (2) anacid such as sulfuric acid, hydrochloric acid, hydrobromic acid,hydroiodic acid, nitric acid, phosphoric acid and acetic acid. Specificexamples of polyamines are ethylene diamine, propylene diamine,hexamethylene diamine, diethylenetriamine, tetraethylenepentamine, andbis(3-aminopropyl)amine.

Another reactant is an acid salt of a water-soluble polyaminopolyamide.The polyaminopolyamide is derived by reaction of a dicarboxylic acid anda polyalkylenepolyamine in a mole ratio of polyalkylenepolyamine todicarboxylic acid of from about 0.8:1 to about 1.4:1. Particularlysuitable dicarboxylic acids are diglycolic acid and saturated aliphaticdicarboxylic acids containing from 3 through 10 carbon atoms such asmalonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid,suberic acid, azelaic acid and sebacic acid. Other suitable dicarboxylicacids include terephthalic acid, isophthalic acid, phthalic acid andalpha-unsaturated dicarboxylic acids such as maleic acid, fumaric acid,itaconic acid, glutaconic acid, citraconic acid and mesaconic acid. Theavailable anhydrides of the above acids can be used for preparing thewater-soluble polyaminopolyamide as well as the esters of the acids.Mixtures of two or more of the above acid moieties can be employed ifdesired.

A number of polyalkylenepolyamines, including polyethylenepolyamines,polypropylenepolyamines, polybutylenepolyamines and the like can beemployed to produce the polyaminopolyamide. The polyalkylenepolyamineemployed will have two primary amine groups and can be represented aspolyamines in which the nitrogen atoms are linked together by groups ofthe formula --C_(n) H_(2n) -- where n is a small integer greater thanunity and preferably 2 through 6, and the number of such groups in themolecule ranges from two up to about eight. The nitrogen atoms can beattached to adjacent carbon atoms in the group --C_(n) H_(2n) -- or tocarbon atoms farther apart, but not to the same carbon atoms. Polyaminessuch as diethylenetriamine, triethylenetetramine,tetraethylenepentamine, and bis(3-aminopropyl)amine, which can beobtained in reasonably pure form are suitable for preparingwater-soluble polyaminopolyamides. Other polyalkylenepolyamines that canbe used include methyl bis(3-aminopropyl)amine; methylbis(2-aminoethyl)amine; and 4,7-dimethyltriethylenetetramine. Mixturesof polyalkylenepolyamines can be used, if desired.

The above polyalkylenepolyamines can be represented by the formula##STR3## where R₃ is hydrogen or methyl; n is an integer 2 through 6, asabove set forth, and y is an integer 1 through 3. Otherpolyalkylenepolyamines that can be employed and which are not includedin the above formula include 1,4-bis(3-aminopropyl)piperazine and1-(2-aminoethyl)piperazine.

The spacing of an amino group on the polyaminopolyamide can be increasedif desired. This can be accomplished by substituting a diamine such asethylenediamine, propylenediamine, hexamethylenediamine and the like fora portion of the polyalkylenepolyamine. For this purpose, up to about80% of the polyalkylenepolyamine can be replaced by a molecularlyequivalent amount of diamine. Usually, a replacement of about 50% orless will be adequate.

Temperatures employed for carrying out reaction between the dicarboxylicacid and the polyalkylenepolyamine to form the water-solublepolyaminopolyamide can vary from about 110° C. to about 250° C. orhigher at atmospheric pressure. For most purposes, temperatures betweenabout 160° C. and 210° C. are preferred. The time of reaction will varyinversely with reaction temperatures employed and usually will be fromabout 1/2 to 2 hours. The reaction is desirably continued to substantialcompletion, as determined by the amount of water evolved. In carryingout the reaction, it is preferred to use an amount of dicarboxylic acidsufficient to react substantially completely with the primary aminegroups of the polyalkylenepolyamine but insufficient to react with thesecondary amine groups and/or tertiary amine groups to any substantialextent. This will usually require a mole ratio of polyalkylenepolyamineto dicarboxylic acid of from about 0.9:1 to about 1.2:1. However, moleratios of from about 0.8:1 to about 1.4:1 can be used.

The following example is illustrative of the preparation of a suitablewater-soluble polyaminopolyamide for use as its salt in the preparationof the precondensate.

EXAMPLE A

A water-soluble polyaminopolyamide for use as its acid salt was formedby adding 146 parts (weight) of adipic acid slowly, with stirring, to100 parts (weight) of diethylenetriamine in a reaction vessel equippedwith a stirrer, thermometer and a condenser for collecting waterdistillate. The reaction mixture was stirred and heated at a temperatureof from about 170° C. to 175° C. until amide formation was complete.After air cooling to approximately 140° C., hot water was added withstirring to provide about a 50% solids solution of polyaminopolyamideresin having an intrinsic viscosity of 0.14 measured on a 2% solution inaqueous 1 M NH₄ Cl at 25° C.

The preferred procedure for use in forming the precondensate as setforth in the first step of the process of this invention is describedbelow.

Into a reaction vessel are placed about one mole of dicyandiamide(cyanoguanidine), from about 3/4 mole to about 11/2 moles offormaldehyde, water-soluble polyaminopolyamide in an amount sufficientto provide from about 1/8 to about 1/2 of an equivalent of basicnitrogen (as distinguished from the amide nitrogens of thepolyaminopolyamide), and an acid in an amount equivalent to the amountof the basic nitrogen of the polyaminopolyamide. Suitable acids includesulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, aceticacid, hydrobromic acid and hydroiodic acid. Water is convenientlyemloyed as the reaction medium and sufficient water should be present inthe mixture to provide an aqueous reaction mass that can be easilyagitated (as by stirring) under reaction conditions. The amount of wateremployed is well within the skill of one versed in the art having beforehim the teachings of this invention. The acid forms thepolyaminopolyamide acid salt reactant.

The aqueous mixture is subsequently heated to reflux temperature (about95° C.-105° C.) and refluxed for a period of time of about 15 minutes toabout 30 minutes (or longer, if desired). Subsequently, the ammoniumsalt is added in an amount such that there will be from about 0.7equivalent to about 1.2 equivalents (preferably about 1 equivalent) ofbasic nitrogen derived from the salt of the polyaminopolyamide and theammonium salt present in the reaction mixture. Thus, for example, whenthe polyaminopolyamide is employed in an amount equal to 1/2 (0.5)equivalent of basic nitrogen, the amount of ammonium salt employed willbe such as to provide from about 0.2 equivalent to about 0.7 equivalentof basic nitrogen. The resulting mixture is heated to reflux andmaintained at reflux temperature for about 1 to about 4 hours. Somewhatshorter periods of time can be used if the heating is carried out undermoderate pressure.

In the second step of the process of this invention, there is added tothe precondensate solution from 0.30 to 0.45 mole and preferably from0.35 to 0.40 mole of urea per equivalent of basic nitrogen derived fromthe salt of the polyaminopolyamide and the ammonium salt. The resultingmixture is then heated to about 80° to about 110° C. and maintained atabout 80° to about 110° C. until a solution of modified precondensate isformed. This will usually require a period of time from about 0.5 hourto about 1.5 hours.

In steps (3) and (4) of the process of this invention, there are addedto the modified precondensate from about 1.25 to about 3.75 moles offormaldehyde and the resulting mixture is then heated to between about60° and about 100° C. and maintained thereat until the viscosity of anaqueous solution of the resinous reaction product, when measured at asolids content of 50% at 25° C. is from about U to Z and preferably fromabout V to W, on the Gardner-Holdt scale. This will usually require aperiod of time of from about 20 minutes to about 3 hours. The aqueoussolution is then diluted with water to a solids content of less thanabout 35% and preferably from about 15% to about 25% to terminate thereaction, and the pH is adjusted to from about 6 to about 7.5 to providestorage stability.

If desired, the water-soluble thermosettable resinous compositionsproduced in accordance with the process of this invention can be furthermodified. Post-modification is preferably carried out by diluting thesolution of step (4), if necessary, to a solids content less than 35%,adding to the solution from 0.03 to 0.75 mole and preferably from 0.05to 0.60 mole, per mole of formaldehyde added in step (3), ofepihalohydrin or a nitrogen-containing compound of the formula NHRR',where R and R' are independently hydrogen, alkyl or hydroxyalkyl and,when R is hydrogen, R' is also aminoalkyl or an amido group, heating themixture to about 45° to about 70° C. and maintaining thereat for about0.5 hour to about 2 hours. The nitrogen-containing compounds which canbe used in this step include ammonia, mono- or dialkyl-amines andparticularly alkylamines wherein the alkyl group(s) contain(s) 1 to 4carbon atoms, the mono- or di-alkanolamines, the alkylene diamines andurea. Particularly preferred compounds for the post-modification stepare epichlorohydrin, ammonia, dimethylamine, diethanolamine,ethylenediamine and urea.

The best mode now contemplated for carrying out this invention isillustrated by the following examples of specific embodiments thereofand the invention is not limited to these specific embodiments. Allpercentages are by weight unless otherwise specified and theGardner-Holdt viscosity measurements were made at 25° C.

EXAMPLE 1

Part 1--Into a reaction vessel fitted with reflux condenser, mechanicalstirrer and thermometer were placed the following to provide a mixtureof ingredients:

    ______________________________________                                        Ingredient           Grams                                                    ______________________________________                                        Polyaminopolyamide solution of                                                                     522    (1.24 equivalents                                 Example A (50.6% solids)    of basic nitrogen)                                Formaldehyde (37% aqueous solution)                                                                320    (3.97 moles)                                      Dicyandiamide        269    (3.2 moles)                                       H.sub.2 SO.sub.4 (98%)                                                                             65.5   (.66 mole)                                        ______________________________________                                    

Sulfuric acid was added last and was added dropwise. During addition ofthe sulfuric acid the temperature of the mixture increased to about40°-45° C. The mixture was then heated to a temperature of about 100° C.and refluxed for about 15 minutes. Following cooling of the mixture to85° C., 137.5 grams (1.04 moles) of ammonium sulfate were added and themixture was heated at 100° C. for about 3 hours. The resulting solutionof precondensate weighed 1300 grams and contained 62.5% solids.

Part 2--Into a reaction vessel equipped with a mechanical stirrer,thermometer and reflux condenser were placed 272.4 grams of theprecondensate solution of Part 1 and 15.6 grams (0.26 mole) of urea. Themixture was heated at 100° C. for 1 hour, cooled to 70° C. and then 136grams (1.68 moles) of 37% aqueous formaldehyde were added over a 5minute period. The mixture was maintained at 70° C. until theGardner-Holdt viscosity of the aqueous solution of the resinous reactionproduct was V-W. Water, 600 ml, was added to the reaction vessel and thecontents thereof cooled to room temperature. The pH of the aqueoussolution of the resinous reaction product was adjusted to 7.0 by addingthereto 34 ml of a 25% aqueous solution of sodium hydroxide. Totalsolids was 21.2% and the Gardner-Holdt viscosity of the aqueous solutionwas A-1⁺.

EXAMPLE 2

Part 1--The procedure of Example 1, Part 1 was repeated and gave 1291grams of a precondensate solution having a solids content of 62.1%.

Part 2--Into a reaction vessel equipped with mechanical stirrer,thermometer and reflux condenser were placed 137.1 grams of theprecondensate solution produced in Part 1, above, and 7.8 grams (0.13mole) of urea. The mixture was heated at 100° C. for 1 hour, cooled to70° C. and then 68 grams (0.84 mole) of 37% aqueous formaldehydesolution were added over a 5 minute period. The mixture was maintainedat 70° C. until the Gardner-Holdt viscosity of the aqueous solution ofthe resinous reaction product was W. Water, 150 ml, was added to thevessel and the contents were cooled to 50° C. Next, 3 grams (0.05 mole)of ethylenediamine were added to the vessel and the contents were heatedat 70° C. for 30 minutes, after which time the resulting solution wascooled to room temperature, diluted with 150 ml of water and the pH wasadjusted to 6.9 with 25% aqueous sodium hydroxide. Total solids was22.2% and the Gardner-Holdt viscosity of the diluted solution was B⁺.

EXAMPLE 3

The procedure of Example 2, Part 2 was repeated except that 6.3 grams(0.105 mole) of urea dissolved in 25 ml of water were substituted forthe 3 grams of ethylenediamine and added to the vessel with the contentsat 60° C. Total solids was 21.7% and the Gardner-Holdt viscosity was A⁻.

EXAMPLE 4

The procedure of Example 2, Part 2 was repeated except that followingthe addition of formaldehyde, the mixture was heated at 65° C. until theGardner-Holdt viscosity was W⁺, 12.1 grams (0.21 mole) of 29.4% aqueousammonium hydroxide were substituted for the 3 grams of ethylenediamineand the pH of the diluted solution was adjusted to 7.0. Total solids was21.9% and the Gardner-Holdt viscosity was A⁺.

EXAMPLE 5

The procedure of Example 2, Part 2 was repeated except that 136.2 gramsof the precondensate solution of Example 1, Part 1 were substituted forthe precondensate solution of Example 2, Part 1, 9.7 grams (0.105 mole)of epichlorohydrin were substituted for the ethylenediamine and added tothe vessel with the contents at 60° C., and the pH of the dilutedsolution was adjusted to 7.0. Total solids was 21.7% and theGardner-Holdt viscosity was A-2.

The resinous reaction products produced in accordance with thisinvention are thermosettable and water-soluble. They have particularutility as sizing accelerators for hydrophobic cellulose reactive sizingagents such as acid anhydrides, isocyanates, and ketene dimers.

Hydrophobic acid anhydrides useful as cellulose reactive sizing agentsfor paper include (A) rosin anhydride (see U.S. Pat. No. 3,582,464); (B)anhydrides having the structure ##STR4## where each R₄ is alike ordifferent and is a saturated or unsaturated hydrocarbon radicalcontaining more than 7 and preferably 8 to 30 carbon atoms and ispreferably selected from the group consisting of alkyl, alkenyl,aralkyl, aralkenyl and alkaryl radicals, and (C) cyclic dicarboxylicacid anhydrides having the structure: ##STR5## where R₄ is as abovedefined and R₅ represents a dimethylene or trimethylene radical.Specific examples of anhydrides of formula (I) are myristoyl anhydride,palmitoyl anhydride, oleoyl anhydride, and stearoyl anhydride.Substituted cyclic dicarboxylic acid anhydrides falling within the aboveformula (II) are substituted succinic and glutaric anhydrides such asisooctadecenyl succinic acid anhydride; n-hexadecenyl succinic acidanhydride, dodecyl succinic acid anhydride, decenyl succinic acidanhydride, octenyl succinic acid anhydride, and heptyl glutaric acidanhydride.

Isocyanates that can be used as cellulose reactive sizing agents includerosin isocyanate and isocyanates having the formula R₄ NCO where R₄ isas above defined. Specific examples of such isocyanates are octadecylisocyanate, dodecyl isocyanate, tetradecyl isocyanate, hexadecylisocyanate, eicosyl isocyanate, docosyl isocyanate and6-phenyldecylisocyanate. Polyisocyanates such as 1,18-octadecyldiisocyanate and 1,12-dodecyl diisocyanate wherein one long chain alkylgroup serves two isocyanate radicals and imparts hydrophobic propertiesto the molecule as a whole are also useful.

Ketene dimers used as cellulose reactive sizing agents are dimers havingthe formula:

    [R.sub.6 CH═C═O].sub.2

where R₆ is a hydrocarbon radical, such as an alkyl having at least 8carbon atoms, cycloalkyl having at least 6 carbon atoms, aryl, aralkylor alkaryl. In naming ketene dimers, the radical "R₆ " is named followedby "ketene dimer." Thus, phenyl ketene dimer is: ##STR6## benzyl ketenedimer is: ##STR7## and decyl ketene dimer is: [C₁₀ H₂₁ --CH═C═O]₂.Examples of ketene dimers include octyl, decyl, dodecyl, tetradecyl,hexadecyl, octadecyl, eicosyl, docosyl, tetracosyl, phenyl, benzyl,beta-naphthyl and cyclohexyl ketene dimers, as well as the ketene dimersprepared from montanic acid, naphthenic acid, Δ⁹,10 -decylenic acid,Δ⁹,10 -dodecylenic acid, palmitoleic acid, oleic acid, ricinoleic acid,linoleic acid, linolenic acid, and eleostearic acid, as well as ketenedimers prepared from naturally occurring mixtures of fatty acids, suchas those mixtures found in coconut oil, babassu oil, palm kernel oil,palm oil, olive oil, peanut oil, rape oil, beef tallow, lard (leaf) andwhale blubber. Mixtures of any of the above-named fatty acids with eachother may also be used.

The following examples illustrate the use of the novel resinouscompositions produced in accordance with this invention with a knownketene dimer paper sizing agent. The ketene dimer sizing agent was inemulsion form and contained, prior to dilution, 6.0% of the ketene dimerprepared from a mixture of palmitic and stearic acids and 1.5% ofcationic starch as emulsion stabilizer.

EXAMPLES 6 TO 10

Separate emulsions, each containing 0.10% of ketene dimer and 0.15 % ofone of the resinous reaction products of Examples 1 to 5 were preparedand evaluated in a pulp blend of 40% newsblank, 30% Rayonier bleachedkraft and 30% Weyerhaeuser bleached hardwood kraft pulp beaten to aCanadian standard freeness of 350 cc. The pulp was diluted to 2.55%, theemulsion was added to the dilute stock and the pH was adjusted to 8. Thestock was formed into handsheets with a basis weight of 40 lb./3000 ft.²and the sheets were dried to a moisture content of 3 to 5%. Part of thesheets was given an extra cure of 5 minutes at 105° C. In each case, theamount of emulsion used provided a total of 0.25% ketene dimer plusresinous reaction product, based on dry pulp weight.

The Table below sets forth the size test results on the paper sized inaccordance with Examples 6 to 10 and with a control emulsion containing0.10% ketene dimer and 0.15% of a resin produced according to thegeneral procedure of Example 5 of U.S. Pat. No. 3,840,486, a separatecontrol being used for each series of tests. The resin solution used forthe control had a solids content of 31.4% and was obtained by heating amixture of 136.2 grams of the solution of Example 1, Part 1 and 68 gramsof 37% aqueous formaldehyde at 99° C. until the Gardner-Holdt viscositywas X, adding 100 ml. of 5% aqueous sodium hydroxide and cooling to roomtemperature. All size properties given herein were determined by use ofthe Hercules Sizing Tester using Test Solution No. 2 to 80% reflectance.

                  TABLE                                                           ______________________________________                                               Resinous                                                                             Size Test Results in Seconds (Average                                  Reaction                                                                             of 5 Samples)                                                          Product                     Cured for                                         of     Off      Natural aging                                                                             5 min.                                     Example  Example  Machine  1 day 7 days                                                                              @ 105° C.                       ______________________________________                                        6        1        3        119   206   497                                    CONTROL  --       3        71    101   278                                    7        2        3        51    83    276                                    8        3        3        56    89    327                                    CONTROL  --       4        43    66    114                                    9        4        3        58    94    362                                    CONTROL  --       2        42    55    216                                    10       5        2        29    36    105                                    CONTROL  --       2         8    11     39                                    ______________________________________                                    

The resinous compositions produced in accordance with this invention,when employed in combination with hydrophobic cellulose reactive sizingagents in the internal or surface sizing of paper, accelerate the rateat which sizing develops and provide high ultimate sizing on naturalaging or oven curing. The compositions can be added either separately tothe paper pulp (for internal sizing) or separately to the paper sheet(for external sizing), either before or after addition of sizing agent.Alternatively, the resinous composition and sizing agent can be added atthe same time to the paper pulp or paper sheet as separate aqueousemulsions or as a single emulsion comprised of the two ingredients. Therange of proportions of the sizing agent and the resinous compositioncan vary from about 1:3 to about 3:1 and the amount of resinouscomposition incorporated into the paper sheet will usually be from about0.05% to about 0.5% (preferably from about 0.05% to about 0.25%) byweight based on the dry weight of the paper.

What I claim and desire to protect by Letters Patent is:
 1. A processfor preparing improved water-soluble thermosettable resinouscompositions containing dicyandiamide-formaldehyde condensates whichprocess comprises (1) forming a precondensate solution by refluxing forabout 1 to about 4 hours an aqueous mixture of (a) a base reactionproduct of 1 mole of dicyandiamide, 0.75 mole to 1.5 moles offormaldehyde and an acid salt of a water-soluble polyaminopolyamide inan amount sufficient to provide from about 0.125 to about 0.5 equivalentof basic nitrogen and (b) an ammonium salt in an amount such that therewill be from 0.7 equivalent to about 1.2 equivalents of basic nitrogenderived from the salt of the polyaminopolyamide and the ammonium salt inthe aqueous medium, (2) adding to the precondensate solution from 0.30to 0.45 mole of urea per equivalent of basic nitrogen derived from thesalt of the polyaminopolyamide and the ammonium salt, and heating theaqueous mixture at about 80° to about 110° C. for about 0.5 to about 1.5hours until a solution of modified precondensate is formed, (3) addingfrom about 1.25 to about 3.75 moles of formaldehyde to the aqueoussolution of modified precondensate and (4) heating the resulting mixtureat about 60° to about 100° C. until the viscosity of an aqueous solutionof the resulting reaction product at a solids content of 50% is fromabout U to Z on the Gardner-Holdt scale.
 2. The process of claim 1comprising the additional steps of diluting the solution of step (4), ifnecessary, to a solids content less than 35%, adding from 0.03 to 0.75mole, per mole of formaldehyde added in step (3) of epihalohydrin or anitrogen-containing compound of the formula NHRR' where R and R' areindependently hydrogen, alkyl or hydroxyalkyl and, when R is hydrogen,R' also is aminoalkyl or an amido group and heating the resultingmixture at about 45° to about 70° C. for about 0.5 hour to about 2hours.
 3. The process of claim 1 wherein the salt of thepolyaminopolyamide is the sulfuric acid salt of a water-solublepolyaminopolyamide derived from adipic acid and diethylenetriamine. 4.The process of claim 3 wherein the ammonium salt is ammonium sulfate. 5.The process of claim 4 wherein step (4) is carried out until thereaction product has a viscosity of V to W on the Gardner-Holdt scale.6. The process of claim 5 comprising the additional steps of dilutingthe solution of step (4), if necessary, to a solids content less than35%, adding from 0.03 to 0.75 mole of epichlorohydrin per mole offormaldehyde added in step (3), and heating the resulting mixture atabout 45° to about 70° C. for about 0.5 hour to about 2 hours.
 7. Theprocess of claim 5 comprising the additional steps of diluting thesolution of step (4), if necessary, to a solids content less than 35%,adding from 0.03 to 0.75 mole, per mole of formaldehyde added in step(3), of a nitrogen-containing compound of the formula NHRR' where R andR' are independently hydrogen, alkyl or hydroxyalkyl and, when R ishydrogen, R' also is aminoalkyl or an amido group and heating theresulting mixture at about 45° to about 70° C. for about 0.5 hour toabout 2 hours.
 8. The process of claim 7 wherein the nitrogen-containingcompound is ammonia.
 9. The process of claim 7 wherein thenitrogen-containing compound is urea.
 10. The process of claim 7 whereinthe nitrogen-containing compound is ethylenediamine.
 11. Thewater-soluble thermosettable resinous composition produced by theprocess of claim
 1. 12. An aqueous solution of the composition of claim11 having a solids content of about 15% to about 25% and a pH of fromabout 6 to about 7.5.
 13. The water-soluble thermosettable resinouscomposition produced by the process of claim
 2. 14. An aqueous solutionof the composition of claim 13 having a solids content of about 15% toabout 25% and a pH of from about 6 to about 7.5.